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US20210091435A1 - Terminal coating resin film and power storage device using the same - Google Patents

Terminal coating resin film and power storage device using the same Download PDF

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Publication number
US20210091435A1
US20210091435A1 US17/110,862 US202017110862A US2021091435A1 US 20210091435 A1 US20210091435 A1 US 20210091435A1 US 202017110862 A US202017110862 A US 202017110862A US 2021091435 A1 US2021091435 A1 US 2021091435A1
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US
United States
Prior art keywords
layer
resin film
resins
coating resin
terminal
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Pending
Application number
US17/110,862
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English (en)
Inventor
Takuya Muraki
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toppan Inc
Original Assignee
Toppan Printing Co Ltd
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Filing date
Publication date
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Assigned to TOPPAN PRINTING CO., LTD. reassignment TOPPAN PRINTING CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MURAKI, TAKUYA
Publication of US20210091435A1 publication Critical patent/US20210091435A1/en
Pending legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/183—Sealing members
    • H01M50/19—Sealing members characterised by the material
    • H01M50/197—Sealing members characterised by the material having a layered structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D181/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur, with or without nitrogen, oxygen, or carbon only; Coating compositions based on polysulfones; Coating compositions based on derivatives of such polymers
    • C09D181/04—Polysulfides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/06—Polyurethanes from polyesters
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/117—Inorganic material
    • H01M50/119—Metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/121—Organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
    • H01M50/126—Primary casings; Jackets or wrappings characterised by the material having a layered structure comprising three or more layers
    • H01M50/128—Primary casings; Jackets or wrappings characterised by the material having a layered structure comprising three or more layers with two or more layers of only inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/172—Arrangements of electric connectors penetrating the casing
    • H01M50/174—Arrangements of electric connectors penetrating the casing adapted for the shape of the cells
    • H01M50/176—Arrangements of electric connectors penetrating the casing adapted for the shape of the cells for prismatic or rectangular cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/172—Arrangements of electric connectors penetrating the casing
    • H01M50/174—Arrangements of electric connectors penetrating the casing adapted for the shape of the cells
    • H01M50/178—Arrangements of electric connectors penetrating the casing adapted for the shape of the cells for pouch or flexible bag cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/183—Sealing members
    • H01M50/186—Sealing members characterised by the disposition of the sealing members
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/183—Sealing members
    • H01M50/186—Sealing members characterised by the disposition of the sealing members
    • H01M50/188—Sealing members characterised by the disposition of the sealing members the sealing members being arranged between the lid and terminal
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/183—Sealing members
    • H01M50/19—Sealing members characterised by the material
    • H01M50/193—Organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/183—Sealing members
    • H01M50/19—Sealing members characterised by the material
    • H01M50/198—Sealing members characterised by the material characterised by physical properties, e.g. adhesiveness or hardness
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/543—Terminals
    • H01M50/547—Terminals characterised by the disposition of the terminals on the cells
    • H01M50/55—Terminals characterised by the disposition of the terminals on the cells on the same side of the cell
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/543—Terminals
    • H01M50/552—Terminals characterised by their shape
    • H01M50/553—Terminals adapted for prismatic, pouch or rectangular cells
    • H01M50/557—Plate-shaped terminals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present disclosure relates to a terminal coating resin film used for sealing current output terminals of a power storage device or a power generation device, and a power storage device using the terminal coating resin film.
  • a lithium ion battery in which a battery body is sealed in the above packaging material is referred to as a laminated lithium ion battery.
  • This type of lithium ion battery is provided with current output terminals (which may also be referred to as tab leads).
  • current output terminals which may also be referred to as tab leads.
  • a terminal coating resin film (which may also be referred to as a tab sealant) may be arranged covering part of the outer periphery of the current output terminal (e.g., see PTLs 1 to 3).
  • Fully solid-state batteries are under research and development as next generation batteries replacing lithium ion batteries.
  • Fully solid-state batteries are characterized by usage of a solid electrolyte as an electrolytic substance, without using an organic electrolyte solution. Lithium ion batteries cannot be used under temperature conditions higher than the boiling point of their electrolyte solution (about 80° C.), whereas fully solid-state batteries can be used under temperature conditions higher than 100° C., and can enhance conductivity of the lithium ions when the batteries are used under high temperature conditions (e.g., 100° C. to 150° C.).
  • the present disclosure has been made in light of the issues set forth above and aims to provide a terminal coating resin film having good heat resistance, and a power storage device using the terminal coating resin film.
  • a terminal coating resin film according to the present disclosure is characterized in that it is used for sealing a current output terminal in at least one of a power storage device and a power generation device.
  • the terminal coating resin film comprises a resin composition having adhesion to the current output terminal.
  • the resin composition contains at least one of a thermosetting resin and a thermoplastic resin having a melting point of 160° C. or higher, and does not contain any thermoplastic resin having a melting point of less than 160° C.
  • Terminal coating resin films of conventional art mainly comprise polypropylene, and have a melting point of about 150° C. Therefore, the heat resistance of conventional terminal coating resin films is insufficient if the films are used, for example, in fully solid-state batteries that can have a temperature in the range of 100° C. to 150° C.
  • the terminal coating resin film according to the present disclosure has good heat resistance because it contains at least one of a thermosetting resin and a thermoplastic resin having a melting point of 160° C. or higher, and does not contain any thermoplastic resin having a melting point of less than 160° C. Accordingly, if a power storage device or a power generation device is used under temperature conditions, for example, in the range of 100° C.
  • the melting point herein refers to a peak melting temperature which is calculated according to the method described in JIS K7121-1987. If there are two or more independent melting peaks, the lowest peak melting temperature is used.
  • Power storage devices to which the terminal coating resin film of the present disclosure can be applied may be fully solid-state batteries.
  • the terminal coating resin film may be applied to other power storage devices or power generation devices.
  • thermosetting resin may be at least one selected from the group consisting of polyimide resins, phenol resins, urea resins, melamine resins, unsaturated polyester resins, urethane resins, allyl resins, epoxy resins, furan resins, and silicone resins. These thermosetting resins have good adhesion to the metal material (e.g., aluminum or nickel) configuring the surface of the current output terminal, and have good heat resistance.
  • metal material e.g., aluminum or nickel
  • the thermoplastic resin may be at least one selected from the group consisting of polyester resins (e.g., polyethylene terephthalate (PET) and copolymers thereof, and polyester resins based on PET components), nylons, polyvinyl alcohol resins, polyvinylidene chloride, polyamide resins, polybutylene terephthalate resins, polyphenylene sulfide, polyetherimide, polysulfone, fluororesins, polyamide imide, and acetyl cellulose.
  • PET polyethylene terephthalate
  • polyester resins based on PET components
  • nylons polyvinyl alcohol resins
  • polyamide resins polybutylene terephthalate resins
  • polyphenylene sulfide polyetherimide
  • polysulfone fluororesins
  • polyamide imide acetyl cellulose
  • the terminal coating resin film according to the present disclosure may have a single layer structure or a multilayer structure. If the terminal coating resin film has a single layer structure, the resin composition forming the terminal coating resin film is preferred to be one selected from the group consisting of polyester resins, polyphenylene sulfide, urethane resins, and epoxy resins. Use of a film comprising these resins as a terminal coating resin film can easily achieve an advantageous effect of adhesion to the current output terminal (appropriate fluidity of the resin composition during heat sealing), balanced with insulation properties of the current output terminal (prevention of excessive fluidity of the resin composition during heat sealing).
  • the terminal coating resin film can include a first layer and a second layer.
  • the first layer may comprise a resin which is selected from the group consisting of polyester resins having a melting point in the range of 170° C. to 280° C. and polyphenylene sulfide (PPS) having a melting point in the range of 260° C. to 290° C.
  • the second layer may comprise either a thermosetting resin or a thermoplastic resin having a melting point in the range of 160° C. to 280° C.
  • the second layer is preferred to be formed on a surface of the first layer facing the current output terminal. If PET or PPS having a sufficiently high melting point is used as a resin for forming the first layer, the first layer will not melt at the time of heat sealing and thus good insulation properties may be achieved for the current output terminal.
  • the terminal coating resin film may further include a third layer formed on a surface of the first layer facing away from the surface on which the second layer is formed.
  • the third layer may comprise a thermosetting resin or a thermoplastic resin having a melting point in the range of 160° C. to 280° C.
  • the first layer may comprise a thermosetting resin.
  • the terminal coating resin film is preferred to include a thermosetting resin layer formed at least on one surface of the first layer, and the thermosetting resin layer is preferred to have fluidity which is higher than that of the thermosetting resin forming the first layer. Use of such a configuration can achieve good adhesion to the current output terminal.
  • the present disclosure provides a power storage device (e.g., fully-solid state battery) including a power storage device body, a current output terminal extended from the power storage device body, a packaging material sandwiching the current output terminal between surfaces thereof and holding the power storage device body therein, and the terminal coating resin film set forth above disposed between the current output terminal and the packaging material.
  • a power storage device e.g., fully-solid state battery
  • a terminal coating resin film having good heat resistance, and a power storage device using the terminal coating resin film can be provided.
  • FIG. 1 is a perspective view illustrating a fully solid-state battery that is an embodiment of a power storage device according to the present disclosure.
  • FIG. 2 is a schematic cross-sectional view illustrating an embodiment of a packaging material.
  • FIGS. 3( a ) to 3( c ) are schematic cross-sectional views each illustrating a configuration of an inner layer.
  • FIG. 4 is a schematic cross-sectional view taken along the line IV-IV of FIG. 1 , illustrating a configuration of a tab (a terminal coating resin film and a metal terminal) of the fully solid-state battery.
  • FIGS. 5( a ) to 5( c ) are schematic cross-sectional views each illustrating a configuration of a terminal coating resin film.
  • FIGS. 6( a ) to 6( e ) are schematic diagrams illustrating a method of producing evaluation samples of examples and comparative examples.
  • FIG. 1 is a schematic perspective view illustrating a configuration of a power storage device according to the present embodiment.
  • FIG. 1 shows a power storage device 100 as an example of a fully solid-state battery, referring to which the following description will be provided. It should be noted that a power storage device having a configuration shown in FIG. 1 may be referred to as a battery pack or a battery cell.
  • the power storage device 100 as a fully solid-state battery includes a power storage device body 10 , a packaging material 20 , two metal terminals 30 (current output terminals), and a terminal coating resin film 40 (tab sealant).
  • the power storage device body 10 is a battery body that charges or discharges current.
  • the packaging material 20 is arranged covering surfaces of the power storage device body 10 and in contact with part of the terminal coating resin film 40 .
  • FIG. 2 is a cross-sectional view illustrating an example of a cross section of the packaging material 20 .
  • the packaging material 20 is preferred to have a multilayer structure in which a substrate layer 11 , a first adhesive layer 12 a , a first anticorrosion treatment layer 13 a , a barrier layer (metal foil layer) 15 , a second anticorrosion treatment layer 13 b , a second adhesive layer 12 b , and an inner layer 18 are provided in this order from the outer side toward the inner side (power storage device body 10 side). If the inner layer 18 contains PET and/or a copolymer thereof and has a peak melting temperature in the range of 160° C.
  • the packaging material 20 can satisfy the heat resistance required for the packaging material of the power storage device 100 (fully solid-state battery) used under temperature conditions of 100° C. to 150° C., for example.
  • the copolymer of PET in the present disclosure refers to a copolymer containing units of polyethylene terephthalate and units of another resin. This other resin may be polybutylene terephthalate, for example.
  • the inner layer 18 contains polyethylene terephthalate (PET) and/or a copolymer thereof and has a peak melting temperature in the range of 160° C. to 280° C.
  • PET polyethylene terephthalate
  • the substrate layer 11 is preferred to have a peak melting temperature higher than that of the inner layer 18 . If the substrate layer 11 has a peak melting temperature higher than that of the inner layer 18 , the appearance of the packaging material 20 is prevented from being impaired due to melting of the substrate layer 11 (outer layer) at the time of heat sealing.
  • the inner layer 18 and the substrate layer 11 will be explained as follows.
  • a commercially available crystalline PET film (peak melting temperature: about 255° C.) may be used.
  • the peak melting temperature of the inner layer 18 may be controlled according to the heat resistance required of the inner layer 18 (e.g., activation temperature conditions of the power storage device 100 ).
  • a crystallinity-controlled or unstretched crystalline PET film, or a copolymer film containing units of polyethylene terephthalate and units of another resin, or a PET film containing crystalline PET and amorphous PET may be used.
  • a polyester resin which is based on PET components may be used as a material for the inner layer 18 .
  • Such a polyester resin has structural units derived from ethylene glycol, structural units derived from a terephthalic acid, and other structural units.
  • Dihydric alcohol components from which the structural units of the polyester resin are derived may include neopentyl glycol, 1,4-butanediol, and diethylene glycol.
  • Acid components from which the structural units of the polyester resin is derived may include an isophthalic acid, adipic acid, and sebacic acid.
  • the melting point of the polyester resin can be controlled by controlling the amount of these structural units.
  • a copolymer of PET or a polyester resin based on a component of PET is termed a PET resin.
  • the peak melting temperature of the inner layer 18 may be in the range of 160° C. to 280° C. If the temperature is less than 160° C., heat resistance of the inner layer 18 may be insufficient, and if it exceeds 280° C., the temperature for heat sealing may be excessively high.
  • the lower limit of the peak melting temperature of the inner layer 18 may be 165° C., 175° C., 185° C., 195° C., 200° C., 205° C., 215° C., 225° C. or 235° C.
  • the upper limit of the peak melting temperature of the inner layer 18 may be 275° C., 268° C., 262° C. or 252° C.
  • the inner layer 18 may have a single layer structure, or may have a multilayer structure. As shown in FIG. 3( a ) , the inner layer 18 , if it has a single layer structure, may be a crystalline PET film (peak melting temperature: about 255° C.). Alternatively, a crystallinity-controlled or unstretched crystalline PET film, or a PET resin film having a low peak melting temperature in a range, for example, of 160° C. to 250° C. may be used. If a PET film, or a PET resin film having a low peak melting temperature is used as an inner layer 18 , a crystalline PET film (peak melting temperature: about 255° C.) can be used as a substrate layer 11 .
  • a crystalline PET film peak melting temperature: about 255° C.
  • the inner layer 18 if it has a single layer structure, is preferred to have a thickness in the range of 10 ⁇ m to 100 ⁇ m and more preferably 20 ⁇ m to 80 ⁇ m.
  • a thickness of 10 ⁇ m or more sealing properties and insulation properties may be easily secured, and when it has a thickness of 100 ⁇ m or less, the production cost may be reduced.
  • the inner layer 18 may have a two-layer structure including a first layer 18 a and a second layer 18 b which is formed on an inner surface of the first layer 18 a .
  • the first layer 18 a is preferred to contain PET and/or PET resin and have a peak melting temperature in the range of 170° C. to 280° C.
  • the second layer 18 b is preferred to contain PET and/or PET resin and have a peak melting temperature which is lower than that of the first layer 18 a .
  • the peak melting temperature of the second layer 18 b may, for example, be in the range of 160° C. to 270° C.
  • the difference therebetween is preferred to be 10° C. or more, and more preferably in the range of 20° C. to 100° C.
  • the temperature difference is 10° C. or more, even better sealing strength can be achieved.
  • the first layer 18 a is preferred to have a thickness in the range of 5 ⁇ m to 500 ⁇ m, and more preferably 20 ⁇ m to 200 ⁇ m.
  • the first layer 18 a has a thickness of 5 ⁇ m or more, insulation properties can be easily secured, and when it has a thickness of 500 ⁇ m or less, the production cost can be reduced.
  • the second layer 18 b may contain a thermosetting resin instead of PET and/or PET resin, or may contain both PET and/or PET resin and a thermosetting resin.
  • the thermosetting resin may be a polyimide resin, phenol resin, urea resin, melamine resin, unsaturated polyester resin, urethane resin, allyl resin, epoxy resin, furan resin, or silicone resin. These resins may be used singly or in combination of two or more.
  • the second layer 18 b is preferred to have a thickness in the range of 5 ⁇ m to 500 ⁇ m, and more preferably 20 ⁇ m to 200 ⁇ m.
  • the second layer 18 b has a thickness of 5 ⁇ m or more, sealing properties can be easily secured, and when it has a thickness of 500 ⁇ m or less, the production cost can be reduced.
  • the inner layer 18 may have a three-layer structure including a first layer 18 a , a second layer 18 b , and a third layer 18 c which is formed on a surface of the first layer 18 a facing away from the surface on which the second layer 18 b is formed.
  • the third layer 18 c is preferred to contain PET and have a peak melting temperature which is lower than that of the first layer 18 a .
  • the third layer 18 c may have a peak melting temperature in the range, for example, of 160° C. to 270° C.
  • the difference therebetween is preferred to be 10° C. or more.
  • the temperature difference is 10° C. or more, even better sealing strength can be achieved.
  • the third layer 18 c may contain a thermosetting resin instead of PET and/or PET resin, or may contain both PET and/or PET resin and a thermosetting resin.
  • the thermosetting resin may be a polyimide resin, phenol resin, urea resin, melamine resin, unsaturated polyester resin, urethane resin, allyl resin, epoxy resin, furan resin, or silicone resin. These resins may be used singly or in combination of two or more.
  • the third layer 18 c is preferred to have a thickness in the range of 5 ⁇ m to 500 ⁇ m, and more preferably 20 ⁇ m to 200 ⁇ m. When the third layer 18 c has a thickness of 5 ⁇ m or more, high sealing strength can be easily secured, and when it has a thickness of 500 ⁇ m or less, the production cost can be reduced.
  • the second and third layers 18 b and 18 c may have the same configuration or different configurations.
  • the inner layer 18 may contain, for example, various additives (e.g., a flame retarder, slip agent, anti-blocking agent, antioxidant, light stabilizer, and tackifier).
  • the substrate layer 11 may have a peak melting temperature higher than that of the inner layer 18 .
  • the peak melting temperature of the inner layer 18 refers to that of the layer (e.g., the first layer 18 a ) having a maximum peak melting temperature.
  • the substrate layer 11 is preferred to have a peak melting temperature higher than that of the inner layer 18 by 10° C. or more, and preferably 30° C. or more.
  • the resin film that can be used for the substrate layer 11 and has a peak melting temperature in the above range may be a nylon film, PET film, polyamide film, polyphenylene sulfide film (PPS film), or the like.
  • the substrate layer 11 may be a commercially available film, or may be a coating film (obtained by applying and drying a coating liquid).
  • the substrate layer 11 may have a single layer structure or a multilayer structure, or may be formed by applying a thermosetting resin.
  • the substrate layer 11 may contain, for example, various additives (e.g., a flame retarder, slip agent, anti-blocking agent, antioxidant, light stabilizer, and tackifier).
  • the difference therebetween (T 11 -T 18 ) is preferred to be 20° C. or more, and more preferably in the range of 40° C. to 100° C.
  • the substrate layer 11 is preferred to have a thickness in the range of 5 ⁇ m to 50 ⁇ m, and more preferably 12 ⁇ m to 30 ⁇ m.
  • first adhesive layer 12 a the first anticorrosion treatment layer 13 a , the barrier layer (metal foil layer) 15 , the second anticorrosion treatment layer 13 b , and the second adhesive layer 12 b .
  • These layers have heat resistance equivalent to or exceeding that of the inner layer 18 or the substrate layer 11 .
  • the adhesive layers 12 a and 12 b may have sufficient heat resistance.
  • a known adhesive can be appropriately selected and used, such as a generally used adhesive for dry lamination, an acid-modified thermally adhesive resin, thermosetting adhesive, or the like.
  • the thermosetting adhesive may, for example, be a polyester urethane adhesive, or epoxy adhesive.
  • the barrier layer 15 is a metal layer having electrical conductivity.
  • the material used for the barrier layer 15 may, for example, be aluminum, stainless steel, or the like. However, from the perspective of cost or weight (density), aluminum is preferred.
  • the anticorrosion treatment layers 13 a and 13 b protect the barrier layer 15 .
  • those layers which contain a rare earth element oxide (e.g., cerium oxide), and phosphoric acid or phosphate may be mentioned.
  • the anticorrosion treatment layers 13 a and 13 b are respectively formed on both surfaces of the barrier layer 15 , considering performance. However, from the perspective of cost, only the anticorrosion treatment layer 13 b may be arranged.
  • FIG. 4 is a cross-sectional view taken along the line IV-IV of FIG. 1 illustrating a terminal coating resin film and a metal terminal.
  • two metal terminals 30 , 30 shown in FIG. 1 one is electrically connected to the positive electrode of the power storage device body 10 and the other is electrically connected to the negative electrode thereof.
  • the two metal terminals 30 , 30 are extended to the outside of the packaging material 20 from the power storage device body 10 .
  • the two terminals 30 , 30 may each have a plate-like shape, for example.
  • Metal can be used as a material for the metal terminals 30 .
  • the material used for the metal terminals 30 may be determined considering, for example, the structure of the power storage device body 10 , materials of the components of the power storage device body 10 , and the like.
  • the power storage device 100 is a fully solid-state battery
  • aluminum is preferred to be used as a material for the metal terminal 30 connected to the positive electrode of the power storage device body 10 .
  • copper having a nickel-plated layer on the surface thereof, or nickel is preferred to be used.
  • the metal terminals 30 each have a thickness depending on the size or capacity of the fully solid-state battery. If the fully solid-state battery has a small size, the thickness of each metal terminal 30 may be 50 ⁇ m or more, for example. If the fully solid-state battery has a large size suitable for electrical storage or vehicle installation, the thickness of each metal terminal 30 can be appropriately determined within the range of 100 ⁇ m to 500 ⁇ m, for example.
  • the terminal coating resin film 40 is arranged covering part of the outer periphery of a metal terminal 30 . Arrangement of the terminal coating resin film 40 between the metal terminal 30 and the packaging material 20 can achieve even higher sealing properties and insulation properties for the power storage device 100 .
  • the terminal coating resin film 40 has heat resistance equivalent to or exceeding that of the inner layer 18 or the substrate layer 11 .
  • the terminal coating resin film 40 comprises a resin composition having adhesion to the metal terminal 30 .
  • the resin composition contains at least one of a thermosetting resin and a thermoplastic resin having a peak melting temperature (melting point) of 160° C. or higher, and does not contain any thermoplastic resin having a peak melting temperature of less than 160° C.
  • the terminal coating resin film 40 having such a configuration can sufficiently maintain sealing properties of the power storage device 100 even when the power storage device is used under temperature conditions in the range of 100° C. to 150° C., for example, or even when the temperature of the metal terminal 30 reaches a temperature range of 100° C. to 150° C., for example.
  • the resin composition may contain at least one of a thermosetting resin and a thermoplastic resin having a peak melting temperature (melting point) of 200° C. or higher, and may contain no thermoplastic resin having a peak melting temperature of less than 200° C.
  • thermosetting resin used for the terminal coating resin film 40 may be at least one selected from the group consisting of polyimide resins, phenol resins, urea resins, melamine resins, unsaturated polyester resins, urethane resins, allyl resins, epoxy resins, furan resins, and silicone resins. These thermosetting resins have good adhesion to the metal material (e.g., aluminum or nickel) configuring the surface of the metal terminal 30 , and good heat resistance.
  • metal material e.g., aluminum or nickel
  • the thermoplastic resin used for the terminal coating resin film 40 may be at least one selected from the group consisting of PET, the PET resins mentioned above, nylons, polyvinyl alcohol resins, polyvinylidene chloride, polyamide resins, polybutylene terephthalate resins, polyphenylene sulfide, polyetherimide, polysulfone, fluororesins, polyamide imide, and acetyl cellulose. These thermoplastic resins have good adhesion to the metal material (e.g., aluminum or nickel) configuring the surface of the metal terminal 30 , and good heat resistance.
  • the metal material e.g., aluminum or nickel
  • the terminal coating resin film 40 may have a single layer structure or a multilayer structure. If the terminal coating resin film 40 has a single layer structure (see FIG. 5( a ) ), the resin composition configuring the terminal coating resin film 40 is preferred to be a thermoplastic resin selected from the group consisting of PET, the PET resins mentioned above, polyphenylene sulfide, urethane resins, and epoxy resins, and/or a thermosetting resin selected from the group consisting of urethane resins, and epoxy resins.
  • Use of a film comprising these resins as a terminal coating resin film 40 can easily achieve an advantageous effect of adhesion to the metal terminal 30 (appropriate fluidity of the resin composition during heat sealing), balanced with insulation properties of the metal terminal 30 (prevention of excessive fluidity of the resin composition during heat sealing).
  • the terminal coating resin film 40 may include a first layer 40 a and a second layer 40 b which is formed on the surface of the first layer 40 a facing the metal terminal 30 .
  • the first layer 40 a in this case comprises PET and/or a PET resin having a peak melting temperature in the range of 170° C. to 270° C., or polyphenylene sulfide (PPS) having a peak melting temperature in the range of 260° C. to 300° C.
  • the second layer 40 b comprises a thermosetting resin, or a thermoplastic resin having a peak melting temperature in the range of 160° C. to 270° C. (see FIG. 5( b ) ).
  • the PET or the PET resin forming the first layer 40 a may have a peak melting temperature of 210° C. or higher.
  • the PET or the PET resin forming the second layer 40 b may have a peak melting temperature of 200° C. or higher.
  • SA-SB difference therebetween
  • the first layer 40 a is preferred to have a thickness in the range of 5 ⁇ m to 500 ⁇ m, and more preferably 20 ⁇ m to 200 ⁇ m.
  • the second layer 40 b is preferred to have a thickness in the range of 5 ⁇ m to 500 ⁇ m, and more preferably 20 ⁇ m to 200 ⁇ m.
  • sealing properties can be easily secured, and if it has a thickness of 500 ⁇ m or less, the production cost can be reduced.
  • the film 40 may further include a third layer 40 c which is formed on a surface of the first layer 40 a facing away from the surface on which the second layer 40 b is formed (see FIG. 5( c ) ).
  • the third layer 40 c may comprise a thermosetting resin, or a thermoplastic resin having a peak melting temperature in the range of 160° C. to 270° C.
  • the second layer 40 b is preferred to be made of a thermosetting resin whose fluidity is higher than that of the thermosetting resin forming the first layer 40 a .
  • the third layer 40 c may be made of a thermosetting resin whose fluidity is higher than that of the thermosetting resin forming the first layer 40 a .
  • the third layer 40 c is preferred to have a thickness in the range of 5 ⁇ m to 500 ⁇ m, and more preferably 20 ⁇ m to 200 ⁇ m.
  • the third layer 40 c has a thickness of 5 ⁇ m or more, sealing properties can be easily secured, and if it has a thickness of 500 ⁇ m or less, the production cost can be reduced.
  • a fully solid-state battery has been shown as a power storage device, for example, to which the terminal coating resin film 40 is applied.
  • the terminal coating resin film 40 may be applied to other power storage devices (e.g., lithium ion batteries), or power generation devices.
  • a substrate layer As a substrate layer, a highly heat resistant polyamide film (thickness: 25 manufactured by Unitika, Ltd.) having a peak melting temperature of 300° C. was used.
  • a metal foil layer As a metal foil layer, an aluminum foil (thickness 40 ⁇ m) was prepared.
  • a PET film As an inner layer, a PET film (thickness: 75 single layer structure) having a peak melting temperature of 255° C. was prepared. The substrate layer and the metal foil layer were bonded to each other using a thermosetting adhesive (polyester urethane adhesive), while the metal foil layer and the inner layer were bonded to each other using the same adhesive to thereby obtain a packaging material having sufficient heat resistance.
  • a thermosetting adhesive polyyester urethane adhesive
  • An epoxy resin film (thickness: 100 ⁇ m) was prepared as a terminal coating resin film (single layer structure).
  • a urethane resin film (thickness: 100 ⁇ m) was prepared as a terminal coating resin film (single layer structure).
  • a nylon resin film (thickness: 100 ⁇ m, melting point: 225° C.) was prepared as a terminal coating resin film (single layer structure).
  • a PET film (thickness: 100 ⁇ m, melting point: 225° C.) was prepared as a terminal coating resin film (single layer structure).
  • a polyester copolymer film (thickness: 100 ⁇ m, melting point: 160° C.) was prepared as a terminal coating resin film (single layer structure).
  • a PPS film (thickness: 100 ⁇ m, melting point: 290° C.) was prepared as a terminal coating resin film (single layer structure).
  • a PP film (thickness: 100 ⁇ m, melting point: 140° C.) was prepared as a terminal coating resin film (single layer structure).
  • a two-layer structure terminal coating resin film including a first layer and a second layer was prepared by bonding the following films to each other.
  • Epoxy resin film (thickness: 50 ⁇ m)
  • Second layer PET film (thickness: 50 ⁇ m, melting point: 255° C.)
  • a two-layer structure terminal coating resin film including a first layer and a second layer was prepared by bonding the following films to each other.
  • Second layer Epoxy resin film (thickness: 50 ⁇ m)
  • a two-layer structure terminal coating resin film including a first layer and a second layer was prepared by bonding the following films to each other.
  • Epoxy resin film (thickness: 50 ⁇ m)
  • Second layer Epoxy resin film (thickness: 50 ⁇ m)
  • a two-layer structure terminal coating resin film including a first layer and a second layer was prepared by bonding the following films to each other.
  • First layer PPS film (thickness: 50 ⁇ m, melting point: 290° C.)
  • Second layer PET film (thickness: 50 ⁇ m, melting point: 255° C.)
  • a two-layer structure terminal coating resin film including a first layer and a second layer was prepared by bonding the following films to each other.
  • First layer PPS film (thickness: 50 ⁇ m, melting point: 290° C.)
  • Second layer Epoxy resin film (thickness: 50 ⁇ m)
  • a two-layer structure terminal coating resin film including a first layer and a second layer was prepared by bonding the following films to each other.
  • Epoxy resin film (thickness: 50 ⁇ m)
  • Second layer PP film (thickness: 50 melting point 140° C.)
  • a two-layer structure terminal coating resin film including a first layer and a second layer was prepared by bonding the following films to each other.
  • First layer PP film (thickness: 50 melting point 140° C.)
  • Second layer Epoxy resin film (thickness: 50 ⁇ m)
  • a two-layer structure terminal coating resin film including a first layer and a second layer was prepared by bonding the following films to each other.
  • First layer PP film (thickness: 50 melting point 140° C.)
  • Second layer PET film (thickness: 50 melting point: 255° C.)
  • the packaging material was cut to 120 mm ⁇ 200 mm to prepare samples 50 .
  • the samples 50 were each loaded on a cold forming die so that the inner layer was in contact with the protrusion of the forming machine, followed by deep drawing of 2.0 mm at a forming rate of 15 mm/sec, thereby forming a recess 51 . After that, the samples 50 were each folded in two (see FIG. 6( a ) ).
  • electrodes 58 a and 58 b were respectively connected to the tab 52 and the exposed portion 57 of the metal foil layer of each sample, followed by applying 25 V using a withstand voltage/insulation resistance testing machine (TOS 9201 manufactured by KIKUSUI), and the resistance then was measured (see FIG. 6 ( e ) ).
  • TOS 9201 manufactured by KIKUSUI
  • Measurement samples were prepared as in the above item ⁇ Evaluation of insulation properties>except that no exposed portion 57 of the metal foil layer was formed.
  • a red penetrant manufactured by TASETO Co., Ltd.
  • the samples were unfolded, and presence or absence of the penetrant (degree of red) inside was visually confirmed to evaluate adhesion.
  • the samples were evaluated based on the following criteria, and those samples which were evaluated to be C were determined to be failures. Tables 1 to 4 show the results.
  • Example 2 Example 3
  • Example 4 Terminal Material Epoxy Urethane Nylon PET coating resin resin resin film
  • Type Thermo- Thermo- Thermo- Thermo- setting setting plastic plastic Melting — — 225° C. 225° C.
  • Point Evalu- Insulation B B B B ation properties Adhesion A A A A A
  • Example 6 Example 1 Terminal Material Polyester PPS PP coating copolymer resin film Type Thermoplastic Thermoplastic Thermoplastic Melting 160° C. 290° C. 140° C. Point Evaluation Insulation B B C properties Adhesion A A C
  • Example 11 First Material Epoxy Urethane Epoxy PPS PPS layer resin resin resin 40a Type Thermo- Thermo- Thermo- Thermo- Thermo- setting setting setting plastic plastic Melting — — — 290° C. 290° C. Point Second Material PET Epoxy Epoxy PET Epoxy layer resin resin resin 40b Type Thermo- Thermo- Thermo- Thermo- Thermo- plastic setting setting plastic setting Melting 255° C. — — 255° C. — Point Evalu- Insulation A A A A A ation properties Adhesion A A A A A A A A A A A A A ation properties Adhesion A A A A A A A A
  • Example 4 First Material Epoxy PP PP layer resin 40a Type Thermo- Thermo- Thermo- setting plastic plastic Melting — 140° C. 140° C. Point Second Material PP Epoxy PET layer resin 40b Type Thermo- Thermo- Thermo- plastic setting plastic Melting 140° C. — 255° C. Point Evalu- Insulation B B B ation properties Adhesion C C C
  • a terminal coating resin film having good heat resistance, and a power storage device using the terminal coating resin film can be provided.
  • 10 . . . Power storage device 10 . . . Power storage device; 20 . . . Packaging material; 30 . . . Metal terminal (current output terminal); 40 . . . Terminal coating resin film; 40 a . . . First layer; 40 b . . . Second layer; 40 c . . . Third layer; 100 . . . Power storage device.

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WO2020004412A1 (ja) 2020-01-02
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